Cyanoaryl-thiodiazole-azo dyestuff

ABSTRACT

Azo dyestuff of the formula   IN WHICH X and Y, independently of one another, are alkyl, cycloalkyl, aralkyl, or aryl, and in which X and Y together may form the residual member of a fused aromatic-carbo-cyclic or aromaticheterocyclic ring which may be partially hydrogenated; and K is the radical of a coupling component; and processes for the production of such dyestuffs. These dyestuffs are useful for dyeing and printing synthetic fiber materials such as polypropylene, cellulose acetates, polyurethanes, polyamides and polyesters; the dyeings having good general fastness properties especially better fastness to sublimation.

United States Patent Leverenz CYANOARYL-THIODIAZOLE-AZO DYESTUFF Inventor: Klaus Leverenz, Leverkusen,

Germany Assignee: Bayer Aktiengesellschaft,

Leverkusen, Germany Filed: Feb. 11, 1972 Appl, No.: 225,618

Foreign Application Priority Data Feb. 11, 1971 Germany 2106585 US. Cl 260/158, 8/41 C, 8/41 D, 260/154, 260/155, 260/156, 260/250 R, 260/288 R, 260/293.68, 260/296 R, 260/302 D, 260/304, 260/306.8 D, 260/325,

Int. Cl C091) 39/08, D06p 3/00, D06p 3/52 Field of Search 260/158, 306.8 D, 306.8 R, 260/154, 158

References Cited UNITED STATES PATENTS 12/1968 Sartori 260/158 5/1971 Favre 260/186 3/1973 Cieciuch 'et al 260/158 X Primary Examiner-Floyd D. Higel Attorney, Agent, or Firm--Plumley & Tyner [57] ABSTRACT Azo dyestuff of the formula X CN in which X and Y, independently of one another, are alkyl, cycloalkyl, aralkyl, or aryl, and in which X and Y together may form the residual member of a fused aromatic-carbo-cyclic or aromatic-heterocyclic ring which may be partially'hydrogenated; and

K is the radical of a coupling component; and processes for the production of such dyestuffs. These dyestuffs are useful for dyeing and printing synthetic fiber materials such as polypropylene, cellulose acetates, polyurethanes, polyamides and polyesters; the dyeings having good general fastness properties especially better fastness to sublimation.

5 Claims, N0 Drawings 1 CYANOARYL-THlODIAZOLE-AZO DYESTUFF The subject-matter of the present invention comprises aminothiodiazoles of the formula in which X and Y, independently of one another. stand for alkyl, cycloalkyl, aralkyl or aryl radicals, and in which X and Y together may form the residual members of a fused aromatic-carbocyclic or aromatic-heterocyclic ring which may be partially hydrogenated,

as well processes for their production.

Suitable aromatic-carbocyclic rings which may be partially hydrogenated are benzene, naphthalene, tetralin, indane, anthracene, phenanthrenc and other rings, the benzene and naphthalene rings being particularly suitable.

These rings may contain further substituents, such as nitro, CFgg, alkyl, cycloalkyl, aralkyl, aryl, halogen, alkoxy, aryloxy, alkylcarbonyl, arylcarbonyl, alkylcarbonylamino, aryl-carbonylamino, alkylsulphonylamino, aryl-sulphonylamino, alkylsulphonyl, aralkylsulphonyl, aryl-sulphonyl radicals and sulphamoyl and carbamoyl radicals which are preferably substituted by alkyl groups.

The aryl radicals mentioned above preferably comprise phenyl and naphthyl radicals.

Suitable alkoxy radicals are mainly those with l 5 carbon atoms.

Suitable alkyl radicals are primarily those with l 5 carbon atoms.

Suitable aralkyl radicals are mainly the henzyland phenylethyl radicals.

A suitable cycloalkyl radical is, for example, the cyclohexyl radical.

Suitable heterocyclic rings formed by X and Y together with the ethylene group are pyridine, quinoline, thiophen, thionaphthene, dibenzofuran and pyrazine rings and, in particular,

s\ 011 on 0H s/CH These rings, too, may carry further substituents, such as, for example, C,-C.,-alkyl radicals, halogen atoms, preferahlychlorine, and optionally substituted phenyl radicals.

A preferred class of aminothiodiazoles according to the invention corresponds to the formula in which A stands for the radicals Rn \N/ 01 R N/ where R means hydrogen, C,-C -alkyl, phenyl, CF;,.

70 halogen, N0 C.-C,-alkylsulphonyl, phenylsulphonyl or C -C -alkoxy; m stands for 1,2 or 3; and it stands for l or 2.

A class of compounds within the scope of the formulae (l) or (ll) which is particularly preferred has the formula (III) It t /k in which R stands for hydrogen, methyl, phenyl, chlorine, N0 CH,-,SO or methoxy, and it stands for l or 2, as well as the compound tained when amino-imino-pyrrolenines of the formulav I NH N32 x x Y N (IV) in which X and Y have the same meaning as above, are reacted in any sequence (a) with hypohalous acids or their salts, and (b) with thiocyanic acid or its salts. A preferred variant of the process is characterised in that, in a first step, amino-imino-pyrrolenines of the formula (IV) are converted by the reaction with hypohalous acids or their salts at temperatures of 30 to 30C, preferably at -l to C, into the corresponding N-halogen compounds of the probable formula I ll N I N-HaI (v) y N u an RE I m2 x N x I \N Y m2 Y NH in which X and Y have the same meaning as above, and these compounds are treated with hypohalous acids or their salts at temperatures of to 30C, preferably at l0 to 10C.

It must be regarded as definitely surprising that these reactions proceed so smoothly under these mild conditions, since, apart from thermolysis which occurs under substantially more drastic conditions, no reactions of pyrrolenines of this type have hitherto been disclosed which proceed with ring cleavage and the formation of a nitrile group; the formation of the new aminothiodiazoles was therefore by no means foreseeable.

The reaction ofthe N-halogen compounds of the formula (V) with thiocyanic acid or its salts to form the aminothiodiazoles of the formula (I) can be carried out in an aqueous, organic or aqueous-organic medium. As the reaction is exothermic, cooling of the reaction mixture may be necessary. depending on the type of reaction components. Suitable organic solvents are primarily those which are largely inert towards the reaction components in the above-mentioned preferred temperature range from about 0to 50C. Solvents which have proved particularly satisfactory are alcohols, such as methanol, ethanol, nand i-propanol, n-, iand ten.- butanol; ethers such as diethyl ether, di-isopropyl ether, di-isobutyl ether, methyl glycol, ethyl glycol and dioxan; acid amides such as dimethyl formamide, dimethyl acetamide, N-methyl-pyrrolidone, tetramethylurea. hexamethyl-phosphoric acid trisamide; furthermore, tetramethylene-sulphone, dimethyl sulphoxide, tetrahydrofuran, nitromethane, nitropentane, odichlorobenzene, nitrobenzene, pyridine, methylpyridine, quinoline, methyl-quinoline, as well as mixtures of these solvents. I i

arson The expedient procedure for carrying out this reac- I tion in practice consists in slurrying a N-halogen compound (V) with a suitable solvent, for example. methanol, at room temperature; then adding the equivalent amount of a salt of thiocyanic acid, for example. NH,SCN, in powdered form or as an aqueous or methanolic solution, with stirring and possibly with cooling. in such a manner that the temperature does not exceed 50C; and then, if necessary, completing the reaction by heating to 60 C or by boiling under reflux. The reaction is completed when a sample acidified with acetic acid no longer leads to spontaneous discoloration of Kl-starch paper. The reaction products are precipitated or they are isolated by conventional methods of working up, such as precipitation with water or concentration of the solution.

The N-halogen compounds of the formula (V) required as starting materials are new and are therefore likewise a subject-matter of the present invention. These highly reactive compounds are colourless to yellow crystalline, sometimes also amorphous, substances melting almost exclusively with decomposition, mostly above 200C. These compounds are obtained by I known methods for the preparation of N-halogen compounds (cf. e.g., Houben-weyl: Methoden der organischen Chemie," Vol. V/3, 796, and V/4, 32) by reacting amino-imino compounds of the formula (IV) or their salts (with the exceptionof the thiocyanates) with organic or inorganic hypohalites in suitable solvents and,- advantageous'ly, in the presence of acid-binding agents, at temperatures of 25 to 25C, preferably at l0 to 10C; it is of no importance for the desired course of the reaction whether the hypohalite is prepared separately and added to (IV) or whether elementary halogen is caused to react on a solution or suspension of (lV) and an acid acceptor.

Suitable reaction media in which N-halogenationis carried out are water and/or water-miscible solvents such as methanol, tert.-butanol, dimethyl formamide,

dimethyl acetamide, N-methyl-pyrrolidone, hexameth-- 5 l-amino-3-imino-5(6)-cyclohexyl l-amino-3-imino-5(6)-phenyll-amino-3-imino-5(6)-B-naphthyll-amino-3-imino-4,5,o,7-tetrahydrol-amino-3-imino-4(7)-chlorol-amino-3-imino-5(6)-chlorol-amino-3-imino-5,6-dichlorol-amino-3-imino-4(7)-nitrol-amino-3-imino-5(6)-nltr0- l-amino-3-imino-5(6)-methoxyl -amino-3-imino-5( 6)-ethoxyisoindolenine, l-amino-3-imino-5( 6)-benzyloxyisoindolenine, l-amino-3-imino-5(6)-phenoxyisoindolenine, lamino-3-imino-5(6)-methylmercaptoisoindolenine, l-amino-3-imino-5(6)-phenylmercaptoisoindoleninc. l-amino-3 -imino-5(6)-benzylmercapto-isoindolenine. l-amino3-imino-5(6)-methylsulphonyl-isoindolenine. l-amino-3-imino-5( 6 l-cthylsulphonyl-isoindolenine. l-umino-3-imino-5(6)- benzylsulphonyl-isoindolenine, l-amino-3-imino-5(6)- phenyl-sulphonyl-isoindolenine. l-amino-3-imino- 5(6)-acetylamino-isoindolenine, l-amino-3-imino- 5(6)-benzoylamino-isoindolenine, l-amino-3-imino- 5(6)-(methylcarbonyl)-isoindolenine, lamino-3- imino-5(6)-(phenyl-carbonyl)-isoindolenine, l-amino- 3-imino-5(6)-trifluoromethyl-isoindolenine, l-amino- 3-imino-5(6)-cyan0-isoindolenine, l-amino-3-imino- 5(6)-methoxycarbonylisoindolenine, l-amino-3-imin0- 5t6)-phenoxysulphonyl-isoindolenine, l-amino-3- imino-5(6)-dimethylaminc-carbonyl-isoindolenine, lamin0-3-imino-5t 6 )-piperidyl-N-sulphonylisoindolenine, l-amino-3-imin0-5(6J-pyridyl-(3')- isoindolenine, l-amino-3-imino-5(6)-[6'-methylbenzothiazolyl-(Z'H-isoindolenine, l-amino-3-imino- 4,5(6,7)-benzois0indolenine, l-amino-3-imin0-5,6- benzo-isoindolenine, l-amin0-3-imino-4( 7 )-azaisoindolenine. l-am ino-3-imino-4,7-diazaisoindolenine, l-amino-3-imino-4(7)-aza-5(6)-phenylisoindolenine, l-amino-3-imino-4,7-diaza-5,6-dimethyl-isoindolenine. l-amin0-3-imino-4,7-diaza-5,6-diphenyl-isoindolenine, l-amino-3-imino-4,7-dithia-4,5,6,7- tetrahydro-isoindolenine and compounds of the formulae:

isoindolenine, isoindolcnine, isoindolenine, isoindolenine, isoindoleninc, isoindolenine. isoindolenine, isoindolenine, isoindolenine. isoindoleninea isoindolenine,

x ON

Will

and subsequent reaction with ammonia or by an ureamelt of the corresponding dicarboxylic acids.

Suitable o-dicarboxylic acid nitriles (Vll) are: phthalodinitrile, 3-chloro-phthalodinitrile, 4-chloro' phthalodinitrile, 4,5-dichloro-phthalodinitrile, 4- mcthyl-phthalodinitrile. 4-cyclohexyl-phthalodinitrile. 4-tcrt,-butyl-phthalodinitrile, 4-phenylphthalodinitrile. 4-(nuphthyl-Z'l-phthalodinitrile, 4- (pyridiyl-(3')-phthalodinitrile, 4-[6-methylben2thiazolyl-( 2' I-phthalodinitrile, l.2,5,6-tetrahydrophthalodinitrile, 4-methyll ,2,5.6-tetrahydrophthalodinitrile, 4-methoxy-phthalodinitrile. 4-ethoxyphthalodinitrile, 4-phenoxy-phthalodinitrilc. 4-methylmercapto-phthalodinitrile, 4-benzylmercaptophthalodinitrile, 4-phenylmercapto-phthalodinitrile, 4-methyl-sulphonyl-phthalodinitrile, 4-ethylsulphonylphthalodinitrile, 4-benzylsulphonyl-phthalodinitrile, 3-nitro-phthalodinitrile, 4-nitro-phthalodinitrile, 4- phenylsulphonyl-phthalodinitrile, 4-acetylaminophthalodinitrile, 4-benzoylamino-phthalodinitrile, 3,4- dicyano-acetophenone, 3,4-dicyano-propiophenone, 3,4-dicyano-benzophenone, 3.4-dicyano-flu0renone, l,2-dicyano-naphthalcne, 2,3-dicyanonaphthalene, 4- trifluoromethyl-phthalodinitrile, 1,2,4-tricyanobenzene, 3,4-dicyano-benzoic acid ethyl ester, 3,4-dicyano-benzene-sulphonic acid phenyl ester, 3,4- dicyanobenzoic acid diethylamide, 3,4-dicyanobenzoic acid morpholide, 3,4-dicyano-benzoic acid pyrrolidide; 3,4-dicyano-benzene-sulphonic acid diethylamide, 3,4-dicyano-benzene-sulphonic acid morpholide, 2,3-dicyano-pyridine, 3,4-dicyano-pyridine, 2,3- dicyano-o-phenyl-pyridine, 3,4-dicyano-6phenylpyridine, 3,4-dicyano-6-phenyl-pyridinc, 3,4-dicyano- 2-methyl-o-phenyl-pyridine, 2,3-dicyano-quinoline, 2,3-dicyano-pyrazine, 2,3-dicyano-6-phenyl-pyrazine, 2,3-dicyano-5,6-dimethyl-pyrazine, 2,3-dicyano-5,6- diphenyl-pyrazinc, 2,3-dicyano-thiophen, 2,3-dicyanothlonaphthene, 3,4-dicyano-diphenyloxide, 3,4- dicyanodiphenylsulphide, 4,5-dicyano-l-methy1- imidazole and compounds of the formulae free bases of the formula (IV) or alkoxy-imino compounds of the formula O-ailcyl n N Y Y -alky3l. NE

in which X and Y have the same meaning as above;

and

alkyl stands for a C,-C.,-alkyl radical, with NH.,SCN in, for example, an alcoholic solution or suspension.

The alkoxy compounds of the formula (Vlll) can be prepared. for example. according to the process described in German Pat. Specification No. 879,102.

This second process variant can likewise be carried out as a single-pot reaction, but after the reaction of (IV) with NH SCN care must be taken to remove the liberated ammonia as completely as possible. in order to obviate its reaction with hypohalites.

A particularly advantageous method of carrying out the process for the production of the new aminothiodiazoles (1) according to the invention consists in the base catalysts are added in a single-pot reaction to solutions or suspensions of the dinitriles (VII) in an alcoholic solvent at 0 to 60C, preferably at 15 to C; when the reaction is completed [this is established according to an acidimetric process described in J. Org. Chem. 26,412 (1961)], approximately the equimolar amount of ammonium thiocyanate [referred to (VII)] is added at room temperature with stirring; if necessary, the mixture is boiled under reflux for some time, in order to complete the reaction; it is then cooled to 10 to 0C; and the amount of hypohalite calculated for the formulation of the desired aminothiodiazole is added dropwise in an aqueous or organic solution.

Of course. the hypohalite solution can also be prepared in the reaction vessel itself in that the calculated amount of chlorine or bromine is allowed to act subsequently to the thiocyanate reaction and after the addition of one equivalent of alkali metal or alkaline earth metal hydroxide or alcoholate in an aqueous or alcoholic solution.

The new S-amino-l,2,4-thiodiazoles of the formula (1) are colourless to yellow crystalline substances I which are suitable. inter alia, for the production of valuable azo dyestuffs.

A further subject-matter of the present invention comprises azo dyestuffs of the general formula in which X and Y, independently of one another, stand for al-.

kyl, cycloalkyl, aralkyl or aryl radicals, and in which X and Y together may form the residual members of a fused aromatic-carbocyclic or aromatic-heterocyclic ring which may be partially hydrogenated; and K represents the radical ofa coupling component, as well as their production and their use for the dyeing and printing of synthetic organic materials.

(VIII) Suitable aromatic-carbocyclic rings which may be partially hydrogenated are benzene, naphthalene, tetralin, indane, anthracene, phenanthrene and other rings, the benzene and naphthalene rings being particularly suitable.

These rings may contain further'subs'tituents, such nitro, 'CF;,, alkyl, cycloalkyl, aralkyl, aryl, halogen, alkoxy, aryloxy, alkylcarbonyl, arylcarbonyl, alkylcarbonylamino, arylcarbonylamino, alkylsulphonylamino, aryl-sulphonylamino, alkyl-sulphonyl, aralkylsulphonyl, aryl-sulphonyl radicals and sulphamoyl and carbamoyl radicals which are preferably substituted by alkyl groups.

Suitable heterocyclic rings formed by X and Y together with the ethylene group are pyridine, quinoline, thiophen, thionaphthene, dibenzofuran and pyrazine rings, as well as, in particular.

These rings, too, may carry furthe r substituents such as, for example, C -C -alkyl radicals, halogen atoms, preferably chlorine, and optionally substituted phenyl radicals.

Suitableradicals K are, for example, radicals of coupling components of the benzene, naphthalene, pyrazole, acyl-acetic acid amide, pyrimidine, pyridine, thiazole, indole, imidazole, indazole and quinoline series which may carry non-ionic and/or cationic substituents, as well as radicals of enolisable aliphatic ketones.

The term non-ionic substituents" refers to radicals commonly used in dyestuff chemistry, for example, C,- C alkyl, C,-C -alkoxy, C -C -alkyl-carbonylamino, arylazo radicals and halogen atoms such as fluorine, chlorine and bromine.

Suitable cationic substituents' are primarily ammonium groups. I

9 Suitable arylazo radicals are primarily phenylazo radicals which may also carry non-ionic substituents.

A preferred group of azo dyestuffs within the scope of the formula (1 corrcsponds to the formula I n-a a I/ l (2) in which Z, means hydrogen, alkyl or aralkyl;

Z means Z or aryl',

Z means hydrogen, halogen, alkyl, alkoxy or aryloxy;

Z means hydrogen, alkyl, alkoxy, cyano, halogen or acylamino; and

A stands for the radicals m iky N\ R--E- or R n N/ n \N/ in which R means hydrogen, C,-C.,-alkyl, phenyl, CF

where W preferably stands for C -C -alkyl, phenyl or benzyl radicals, W for H or C,-C -alkyl.

Suitable substituents in the alkyl groups are, furthermore, ammonium groups such the trimethyl ammonium. benzyl-dimethyl ammonium. allyl-dimethyl ammonium, pyridinium, imidazolium, triazolium and dimethyl hydrazinium groups.

Suitable aralkyl radicals Z, and Z are benzyland phenylethyl radicals.

Suitable aryl radicals Z, are phenyl radicals which may be substituted by alkyl, alkoxy or halogen.

Suitable alkyl and alkoxy radicals Z and Z are methyl. ethyl, CF methoxy and ethoxy.

Suitable aryloxy radicals 2,, are optionally substituted phenoxy radicals.

Suitable acylamino radicals where the acyl portions are the formyl radical; C -C -alkylcarbonyl radicals which may be substituted in the alkyl radical by fluorine, chlorine. bromine, cyano, C -C -alkoxy, phenoxy or C,-C -alkyl-carbonyloxy; aralkyl-carbonyl radicals such as benzyl-carbonyl; aryl-carbonyl radicals such as phcnyLcarbonyI, tolyl-carhonyl, liiryl-carhonyl. thicnyl-carbonyl or pyridyl-carbonyl', methyland ethylsulphonyl radicals; aryl-sulphonyl radicals such as phenylsulphonyl or p-tolyl'sulphonyl; the radical of a carbonic acid monoester such as methoxy-carbonyl or phenoxy-carbonyl; the radical ofa carbonic acid monoamide such as amino-carbonyl, dimethylaminocarbonyl, cyclohexylaminc-carbonyl and phenylaminocarbonyl; as well as the radical of a sulphonic acid monoamide such as dimethylamino-sulphonyl.

Dyestuffs which are particularly preferred are those of the formula l 2' Ls 1 xn in which R stands for hydrogen, methyl, phenyl, chlorine or methoxy, N0 CH ',SO

m stands for l, 2 or 3;

Z and Z-;, independently of one another. stand for hydrogen, methyl, ethyl, n-propyl, n-butyl, chloroethyl, cyanoethyl, hydroxyethyl, methylcarbonyloxyethyl, methoxycarbonyloxyethyl, ethoxycarbonyloxyethyl, methoxycarbonylethyl or ethoxycarbonylethyl;

Z2, stands for hydrogen, chlorine. methyl. methoxy,

ethoxy or phenoxy; and

Z stands for hydrogen, chlorine. methyl. methoxy,

acetylamino or propionylarnino, those of the formula 13 carbonylamino)-anilinc, N,N-dimcthyl-3-(phenoxycarbonylaminol-aniline, N,N-diethyl-3(fi-chloropropionylamino)-aniline, N,N-diethyl-3-(dimethylaminosulphonylamino)-aniline, N,N-diethyl-2-methoxy-5- acetylamino-aniline, N,N-bis-(B-acetoxy-ethyU-Z- ethoxy-S-acetylamino-aniline, N,N-dimethyl-2- phenoxy--formylamino-aniline, N-(B-hydroxyethyl)-' 2-methyl-5-acetylamino-aniline, N,N-diethyl-2,5- dimethoxy-aniline, diphenylamine, N-(methylor ethyl)-diphenylamine, 3-acetylaminodiphenylamine, N-methyl-4-ethoxy-diphenylamine, N-(methylor ethyll-N-(B-acetoxyethyl)-3-acetylaminoaniline. N- (methylor ethyl)-N-(fi-carbomethoxyethyl)-3- acetylamino-aniline, N,N-diethyl-3-hydroxy-aniline.

Suitable coupling components from the series of amino-naphthalenes are, for example, 1- or Z-aminonaphthalene, l-N-(B-hydroxyethyl )-aminonaphthalene, l-phenylaminonaphthalene, 2-amino-8- hydroxy-naphthalene, 2-aminonaphthalene-5- or 6- sulphonic acid dimethylamide.

Further suitable coupling components are: indole, Z-methyl-indole, 2,5-dimethyl-indole, 2,4-dimethyl-7- methoxy-indole, 2-phenyl-indole, Z-phenyl-S-ethoxyindole, Z-methyl-S-or -chloro-indole, l,2-dimethylindole, l-methyl-Z-phenylindole, 2-methyl-5-nitroindole, 2-methyl-5-carbomethoxy-indole, Z-methylindoline, l,2,3,4-tetrahydroquinoline and its derivatives, such as N-ethyl-l ,2,3,4-tetrahydro-quinoline, N-

I (B-hydroxyethyU-l,2,3,4-tetrahydroquinoline, N- benzyl-l ,2,3,4-tetrahydroquinolin e, N-(B- acetoxyethyl l ,2,3,4-tetrahydroquinoline, N-(B- cyanoethyl )-7-acetylamino-l ,2,3,4- tetrahydroquinoline; pyrazolines such as e.g., 3-methylpyrazolone-(S), l-phcnyl-3-mcthyl-pyrazolone-(5). l- (fi-cyanocthyl )-3-methyl-pyrazolonc-( 5 l,3-dimethylpyrazolone-(S), l-(B-acctoxycthyl)-3-methylpyrazolone-t S l-( o-chlorophcnyl )-3-methylpyrazolonc-( 5 l-phenyl-3-carbomcthoxy-pyrazolone- (5), l-phenyl-S-amino-pyrazole, l-(3-aminophenyl)- pyrazolone-( 5 l-( 4-aminophenyl )-pyrazolone-( 5 3-methyl-pyrazolonc-( 5 )-carboxylic acid-( I l-amidine, l-phenyl-pyrazolone-( 5 )-carboxylic acid-( 3 )-amide, 2-methyl-4H-pyr'azolol 2,3-al-bcnzimidazole, [l-( 3- thia-cyclopentyl )-3-methyl pyrazolone-l 5 )-S-dioxide]; pyridines such as 2,fi-dihydroxy-3-cyano-4-methylpyridine, N-(methyl-, ethylor phenyU-h-hydroxy-3- cyano-pyridone-(Z); quinolines such as X-hydroxyquinoline, 2,4-dihydroxy-quinolinc, N-(methyL or nbutyl)-4-hydroxy-quinolone-(2); pyrimidines such as barbituric acid or 2,6-bis-methylamino-4-phenylamino-pyrimidine, 2-ethylamino-4-phenylamino-6- phenoxy-pyrimidine, 2,4-bis-ethylamino-6- phenylamino-pyrimidine, imidazole, 4,5-dimethylimidazole, 4,5 -diphenyl-i'midazole, 4-methyl-imidazole, 4-phenyl-imidazole; thiazoles such as 2-hydroxy-4- [methylor phenyl]-thiazole, 2'methylamino-[4- methyl or -phenyll-thiazole, 2-(B-cyanoethylamino)- [4-methylor phenyll-thiazole.

Instead of a homogeneous diazo component, there may be used a mixture of two or more of the diazo components according to the invention, and instead ofa homogeneous coupling component, there may be used a mixture of two or more of the coupling components according to the invention.

The diazotisation of the diazo components (5) can be carried out, for example, in inorganic or organic acids with sodium nitrite or nitrosyl-sulphuric acid, preferably at l0 to 10C. The preferred inorganic acids are concentrated phosphoric or sulphuric acid, the preferred organic acids are glacial acetic acid and propionic acid, or mixtures of these acids.

Coupling can likewise be carried out in known manner, for example, in a neutral to acidic medium, optionally in the presence of sodium acetate or other buffer substances. The coupling component is preferably added as a solution in phosphoric acid, sulphuric acid, glacial acetic acid or propionic acid or in mixtures of these acids, or as a solution in an organic watermisciblc solvent such as c.g., methanol, ethanol, nor i-propanol, ethylene glycol, ethylene glycol monoalkyl ethers, dioxan, tetrahydrofuran or sulpholane, to a solution of the diazo compound at about 0C with cooling. After about 0.5 to 2 hours, the coupling mixture is poured into ice-water and the reaction is completed by the addition ofa base such as sodium acetate or sodium hydroxide.

The coupling can also be carried out by combining the components in a mixing nozzle. This term refers to a device which permits of mixing the solutions of the diazo component, on the one hand, and the coupling component, on the other hand, in a comparatively small space. At least one ofthe two solutions, is passed through a nozzle, preferably under increased pressure. The mixture of the liquids is expediently poured immediately into ice water while stirring and, if necessary, the coupling is completed by raising the pH value.

Those dyestuffs of the formula (I) in which K contains an arylazo group, are obtained by diazotising monoazo dyestuffs of the formula a Oil 1 I y N ('7) I v sJk NN-K' in which X and Y have the same meaning as above; and K stands for the radical of a coupling component containing a diazotisable amino group, and coupling the product with a suitable coupling component such as a phenol or naphthol.

The monoazo dyestuffs of theformula (7) are obtained by coupling diazotisable amines of the formula (5) with arylamines ofthe formula Ar-NH such as, for ex-ample, aniline, naphthylamine-l,3-toluidine, 2,5- dimethoxy-aniline, and others. Y

The new water-insoluble dyestuffs, their mixtures with one another, and their mixtures with other dyestuffs are eminently suitable, especially in finely divided form, for the dyeing of synthetic fibres and fabrics of, for example, polypropylene, especially polypropylene modified with metals, such as e.g., nickel; cellulose triand 2 /z-acetate; polyurethanes; and, in particular, polyamides such e.g., polycaprolactam, polyhexamethylene-diamine adipat c, or poly-e-aminoundecanoic acid; as well aromatic polyesters such as polyethylene terephthalate and poly-l ,4- cyclohexanedimethylene terephthalate. The dyestuffs according to the invention which contain an ammonium group in the molecule are particularly suitable for the dyeing offlbr'es and fabrics of polyacrylonitrile or of copolymers of-acrylonitrile and other vinyl compounds such as acrylic esters, acrylamides, vinyl chloride, vinylidene chloride and vinyl-pyridine, or of copolymers of dicyano-ethylene and vinyl acetate, as well for the dyeing of acid-modified polypropylene, polyester or polyamide fibres.

For dyeing from an aqueous bath, the water-insoluble dyestuffs are expediently used in dispersed form. Suitable dispersing agents are, for example, sulphite cellulose waste liquor, dinaphthyl-methane-sulphonate, or condensation products of cresol, 2-naphthol-6- sulphonic acid and formaldehyde. Other dispersing and/or wetting agents may be added to the dyebath.

When aromatic polyester fibres or triacetate fibres are dyed at temperatures of up to 105C, it is generally advantageous to add conventional carrier substances in order to attain good dyestuff yields.

The dyeing of polyester materials with the dyestuffs according to the invention can also be carried out according to the known thermofixing process.

For dyeing metal-modified polyolefme fibres, those dyestuffs of the formula (1) are particularly suitable which carry in the coupling component in the 0- position to the azo group a group capable of forming a chelate, for example, 21 OH-, NH or NH-group.

The new water-insoluble dyestuffs can also be used for the spin-dyeing of polyamides, polyesters, polyurethanes and polyolefines.

Printing is likewise carried out in known manner. For this purpose there is used, for example, a printing colour containing, in addition to the dyestuff, the auxiliaries conventionally used in printing, and this printing colour is applied to the materials to be printed and fixed by a subsequent heat treatment.

The dyeings and prints so obtained are characterised by good general fastness properties.

Compared with the most closely comparable dyestuffs of German Pat. Specification 927,944 and of Deutsche Offenlegungsschrift (German Published Specification) 1,909,107, the dyeings with the dyestuffs prepared according to the invention on polyester materials, such as cellulose triand 2V2-acetate as well as polyethyleneterephthalate, are distinguished in particular by a better fastness to sublimation.

The dyestuffs with an ammonium group in the coupling component obtained according to the present process preferably contain, an anion, the radical of a strong acid, for example, sulphuric acid or its semicster, or of an aryl-sulphonic acid, of phosphoric acid, or a halogen ion. The above anions which have been introduced into the dyestuffs molecule according to the present process may be replaced with anions of other acids, e.g. of organic acids such as formic acid, acetic acid, lactic acic or tartaric acid. The dyestuff salts may also be used in the form of double salts, especially with zinc chloride.

Dyeing of polyacrylonitrile, copolymers of acylonitrile and of acid-modified polyolefins, polylamide and polyester materials with dyestuffs containing ammonium groups is generally carried out in an aqueous, neutral or acidic medium at boiling temperature under atmospheric pressure, or in a closed vessel at elevated temperature and under increased pressure. Commercial levelling agents may be used.

Water-insoluble dyestuffs of the general formula (1) which contain one or more alkyl radicals with 4 12 carbon atoms are in many cases suitable for dyeing synthetic fibre materials from organic solvents. The process is characterised in that the fibre materials are impregnated with dyeing liquors containing these dyestuffs and are subsequently subjected to a heat treatment.

Example 1(a):

Preparation of N- chloro-diimino-phthalimide.

58.4 g 1-amino-3-imino-isoindolenine are dissolved in 400 ml of ice-water with the addition of 4 g acetic acid. 102.8 ml of a sodium hypochlorite solution containing 150 g/litre of active chlorine are added thereto dropwise at 0 5C within about 60 minutes. Stirring is continued for 2 hours, the pH is adjusted to 7 8 by means of acetic acid, the precipitate is filtered off and thoroughly washed with water. For purification, the product is stirred once or several times with methanol in order to remove any adhering starting material. After drying at room temperature in a vacuum, there is obtained a white powder which melts at 3 10 315C with decomposition, eliminates iodine from an acetic acid potassium iodide solution, and the NMR-spectra of which indicate the following constitution:

Yield appr.

When this compound is dissolved hot in concentrated acetic acid, a colourless substance of melting point 222 223C crystallises upon cooling; according to elementary analysis, mixed melting point and IR- spectrum, it is identical with the compound of the formula described in the report of Gescllschaft De utscher Chemiker No. 40, 2709 seq.

Example 2(a):

Preparation of N-bromo-diimino-phthalimide.

37 g bromine are added at about 0C within about 20 minutes to a solution of 24 g sodium hydroxide in 250 ml icewater. 29.2 g 1-amino-3-imino-isoindolenine are subsequently introduced, with the simultaneous addition of ice, at 0-5C. Almost complete dissolution occurs at first, and after about 15 minutes an almost colourless precipitate begins to separate. Stirring is continued for 2 3 hours at 0 10C, the precipitate is filtered off with suction, thoroughly washed with water and then with methanol, and dried at room tempera ture in a vacuum. The product melts at about 330C with decomposition. It is sparingly soluble in water, methanol, ethanol, acetone, benzene and dichlorobenzene, more readily soluble in pyridine, dimethyl formamide, dimethyl sulphoxide and N-methyl-pyrrolidone and corresponds to the formula N-Br Yield: about 85;;-

Example 3(a):

Preparation of 4-methoxy-diimino-N- bromophthalimide 35.2 g l-amino-3-imino-5-(6)-methoxyisoindolenine are stirred in 350 ml methanol, and a solution of 24.6 g potassium hydroxide in 125 ml methanol is added at C. 33.6 g bromine are added at about -1 (1 to 0C dropwise in about minutes while externally Cooling with ice/sodium chloride, and stirring is continued at 0 5C for 2 3 hours. The greygrecn precipitate is filtered off with suction, washed first with water, then with methanol, and dried at room temperature in a vacuum. As crude product the 4- mcthoxy-diimino-N-bromo-phthalimide melts at 244 246C. After recrystallisation from pyridine, the melting point is 250 251C.

The corresponding N-chloro compound can be prepared in the following way:

35,2 g l-amino-3-imino-5-(6)-methoxyisoindolenine are stirred in 300 ml isopropanol and 12.5 ml tert.-butyl hypochlorite are slowly added dropwise at room temperature. The precipitate is filtered off with suction after stirring over night, washed with methanol and dried in a vacuum. The N-ehloro compound is obtained in the form of a grey-green powder which melts at about 250C with decomposition.

Example 4(a):

Preparation of 4-phenyl-diimino-N-bromophthalimide.

When 44.4 g of 1-amino-3-imino-5-(6)-phenylisoindolenine are used in Example 3(a) as starting material, then the corresponding N-bromo compound of melting point 2()9 21 1C (from pyridine) is obtained in the form of a yellowish powder.

Example 5(a):

Preparation of 18 When the starting material is replaced in Example 3(a) with 32.2 g l-amino-3-imino-4,7-dithia-4,5,6,7- tetrahydroisoindolenine, the mixture, after the addition of bromine, is clarified, with active charcoal and the pH adjusted to 7 8, then the corresponding N-bromo compound of the formula lI--- Br of decomposition point 166 167C is again obtained in the form of a yellow powder.

Example 6(a):

7 Preparation of 32.2 g 1-amino-3-imino-4,7-dithia-4,5,6,7-tetrahy dro-insoindolenine are stirred at 0 5C in ml hexamethyl-phosphoric acid-bis-dimethylamide, and 51.4 ml of a sodium hypochlorite solution containing 150 g/litre of active chlorine are added at the same temperature within about 1 hour. Stirring is continued at 0 5C for a further 3 hours, the solution is poured into 300 g of ice-water, and the N-chloro compound formed is precipitated by neutralisation with acetic acid. After stirring in methanol and drying in a vacuum at room temperature, there is obtained a yellow powder of decomposition point C.

Tab lo I N-Cl Table l-Continued NH N-Cl (Br) Clji-0l N-Ol NH NH (Br, (Br,

N-Cl (Br) en -g 11-01 (Br) I! N-Cl (Br) 0 1w N-Cl (Br) N-Cl (Br) N-SOZ N-Cl (Br) N-Cl en -s0 N-Cl (Br) 3 5 H H C C r B l C "m.

Table l- Continued N-Cl (Br) Example 7 (a):

Preparation of the thiocyanic acid salts of the general formula (VI) Method (A):

0.5 mol l-amino-3-imino-isoindolenine are dissolved in 500 ml methanol, and 0.5 mol ammonium thiocyanate are added at room temperature. The thiocyanate separates already after a short time as a yellow precipitate with the evolution of ammonia. The mixture is stirred at room temperature for about 2 hours and if desired, the reaction is completed by gentle heating. The precipitate is filtered off with suction, washed first with methanol, then with ether, and dried in a vacuum. The resultant product melts at 250 -255C with decompt sition.

In an analogous way there are obtained, for example, the thioeyanie acid salts of the corresponding 546)- methoxy compound, melting point 247 249C, and of the 5-(6)-phenyl compound, melting point 246 248C.

Method (B):

0.5 mol phthalodinitrile are stirred in 500 ml methanol, and 2.7 g sodium methylate are added. The phthalodinitrile has dissolved after about 1.5 hours. The mixture is stirred at room temperature for 6 8 hours, and 0.5 mol ammonium thiocyanate are then added. Already after a short time, there begins the formation of a yellowish precipitate which is filtered off with suction after stirring over night. Also in this case, the reaction mixture may be heated for a short time in order to complete the reaction.

The sodium methylate used in the present Example as catalyst can be replaced with other alkali metal or alkaline earth metal alcoholates, such as sodium ethylate, potassium tert.-butylate, calcium ethylate, or with organic bases such as e.g., trimethylbenzyl ammonium hydroxide.

lf the phthalodinitrile is replaced with other 0- dicarboxylic acid nitriles of the general formula (V), it is expedient to establish the optimal amounts of catalyst and optional reaction times by preliminary experiments. For observing this reaction, the process dcseribed by Schaefer and Peter, J. Org. Chem. 26, 412 H961), where the degree of conversion is determined acidimetrically has proved satisfactory.

As a rule, the reaction times will be longer when the phthalodinitriles contain, for example, substituents with the properties of electron donators, such as 4- alkoxy or 4-alkylthio groups. On the other hand, some N-Gl (Br) phthalodinitriles containing electron acceptors as substituents, such as 4-nitro, 4-carboxylic ester or 4-alkyl' or arylsulphonyl groups, react substantially faster. Dicyano-pyridines and dicyano-pyrazines are also highly reactive.

lf the'0.5 mol phthalodinitrile are replaced in Example 7(a), Method (B), with 0.5 mol 4-methoxyphthalodinitrile, the reaction with methanol/sodium methylate requires about 40 hours, whereas only about 2 hours are necessary when 0.5 mol 2,3-dicyanopyridine are used.

Example 8(a):

Preparation of 5-amino-3-(2'-cyanophenyl)-l,2,4- thiodiazole 22.5 g ofthe N-bromo-diimino-phthalimide prepared in Example 2(a) are suspended in 200 ml methanol, and 7.6 g ammonium thiocyanate are added. A thick crystal slurry is formed in an exothermic reaction. The mixture is subsequently heated at boiling temperature under reflux for about 30 minutes in orderto complete the reaction, the precipitate is filtered off with suction after cooling, and washed with water until free from salt. After drying, there is obtained an almost colourless powder of melting point 239 240C; yield about l7 g (85 percent of theory). The substance is sufficiently pure for most purposes, for example, for the preparation of azo dyestuffs. If a higher degree of purity is required, it can be recrystallised, for example, from pyridine. The analytically pure product melts at 240C. (C,,H., N 5 (202) Calc. C: 53.5; H: 3.0; N: 27.7; S: 15.8

Found: C: 53.4; H: 2.9; N: 27.7; S: l5.9

The lR-spectrum shows a marked CN-band at 4.5 a.

The solvent methanol used in the present Example may be replaced, for example, with other alcohols such as ethanol, i-propanol or ethyl glycol, or with pyridine, dimethyl formamide, N-methyl-pyrrolidone or tetramethyl-sulphone. The reaction product may be precipitated with water. Sodium, potassium, calcium or barium thiocyanate are suitable to replace ammonium thiocyanate. TheN-bromo compound can be replaced with equimolar amounts of the N-chloro compound of Example lta).

Example 9(a):

Preparation of 5-aminw3-(2-cyanophcnyl)-1,2,4- thiodiazole in a single-pot process 0.5 mol phthalodinitrile are converted in the thioeyanic acid salt of l-amino-3-imino-isoindolenine in analogy with Example 7(a). Method (B). Without intermediate isolation of the product. the reaction mixture is cooled to l to -C, and 80 g bromine and a solution of 54 g sodium methylate in 400 ml methanol are simultaneously added from 2 dropping funnels at not more than 0C within about 2 hours with intense stir.- ring. Stirring is continued at about 0C for a further 2 hours. the precipitate is filtered off with suction and washed first with methanol, then with water. The 5- amino-fl-t 2'-cyanophenyl l .2.4-thiodiazole described in Example 8(a) is obtained in a good yield (appr. 70 percent) and with a high degree of purity.

Example (u):

Preparation of 5-amino-3-(2-cyano-4'( 5 )-methoxyphenyl )-l ,2,4-thiodiazole Method (A):

25.5 g N-bromo-4-methoxy-diimino-phthalimide (Example 3a) are stirred in 200 ml ethanol and, after the addition of 9.7. g potassium thiocyanate. heated at boiling temperature under reflux for 30 minutes. After cooling to room temperature, the precipitate is filtered off with suction and washed with water until free from salt. Yield about 90 percent. The almost colourless product can be recrystallised from benzene/pyridine (1:2) for purification and then melts at 236 238C. C H N 05 (232) Calc. C: 51.7; H: 3.4; N: 24.2; 0: 6.9; S: 13.8

Found: C: 51.7; H: 3.4; N: 23.9; 0. 7.3; S: 13.8

The lR-spectrum shows a marked CN-band at 4.5 u.

Equally good results are obtained with the use of the equivalent amount of N-chloro-4-methoxy-diiminophthalimide.

Method (B):

23.4 g 5-(6)-methoxy-l-amino-3-iminoisoindolenine hydrogen thiocyanate in 200 ml methanol are cooled to about -10C, and 16 g bromine and a solution of 10.8 g sodium methylate in 100 ml methanol are simultaneously added to this suspension from 2 dropping funnels at not more than 0C and with intense stirring. After stirring at about 0C for 2 hours, the precipitate is filtered off with suction, washed first with methanol. then with water, and dried. After recrystallisation from benzene/pyridine, there are obtained almost colourless crystals which are identical with the product obtained according to Method (A).

Example l2(u):

Preparation of 5-amino-3-(2'-cyano-4'-(5)'-phenylpheny1)- l ,2,4-thiodiazole 30.0 g N-bromo-4-phenyl-diimino-phthalimide (lixample 4a) are reacted in 200 ml methanol with l 1.4 g

calcium thiocyanate tetrahydrate in analogy with Example )(u). There results a yellow precipitate which. 5 after washing with water and drying. can he recrystallised from benzene/pyridine. Melting point 225 228C. (Yield .appr. 75 percent of theory). C, =,H ,N S (278) Calc. C: 64.7; H: 3.6; N: 20.1; S: 11.5

Found: C: 64.7; H: 3.8: N: 20.015: 1l.o

The lR-spectrum shows a (N-hand at 4.5 u.

If the N-hromo-4-phenyl-diimino-phthalimide is replaced in the present Example with .'.(\.4 g of the con pound of the formula S E N-Br prepared according to Example 5(a), then a thiodiazole of the formula is obtained with a yield of about 80 percent in the form of a yellow powder which melts at 223 224C after 0 recrystallisation frombenzene/pyridine:

Cale. C: 34.7; H: 2.5; N: 23.1; S: 39.7

Found: C; 35.2; H: 2.8; N: 23.1; S: 39.4

The lR-spectrum shows a CN-band at 4.55 a.

The corresponding N-chloro compounds can also be 'used in these Examples with good results.

Further S-amino-l.2,4-thiodiazoles of the general formula (1) which can be prepared according to the instructions of Example 8(a) from the corresponding N- halogen compounds and/or according to Example 7(a)/9(a) from the corresponding o-dicarboxylic acid dinitriles, are assembled in the following Table 11:

Table I l Continued Formula.

c n o CH3SO2 N-SO Table ll-(ontinued .sero No. Formula l ON 16 N Example llb):

8.8 g amino-3-(2'-cyanophenyl)-I ,2,4-thiodiazole are added at about 0 C with stirring to a mixture of 60 ml of 85 percent ortho-phosphoric acid and ml glacial acetic acid. 7.5 ml of 4L2 percent nitrosylsulphuric acid are added at 5 to 2C within about minutes. and the mixture is subsequently stirred at not more than 0C for 4 hours. 0.5 g urea are then added. and stirring is continued at 0C for 30 minutes. A solution of 8 g N-ethyl-N-(p-cyanoethyll-aniline in 30 ml glacial acetic acid is poured to the resultant diazo solution at -5 to 0C within 30 minutes. After a further 30 minutes, the reaction mixture is poured on to 200 g of ice while stirring. whereupon the dyestuff of the formula 0 H I j! 2 5 tk -N N- -N \CH2-CH2-GN separates in the form of a red precipitate. The mixture is diluted with ice and water to a volume of 600 800 ml in all, the dyestuff is filtered off with suction and washed with water until neutral. lt dyes polyester and polyamide fibres in yellowish red shades of good fastness properties, especially good fastness to sublimation.

Valuable dyestuffs are also obtained in an analogous No, A B

l N-ethyl-N-(B-cyanoethyl)-3-methylaniline red 2 N,N'diethyl-aniline bluish red 3 N-(B'cyanoethyD-aniline yellowish red 4 N-(B-cyanoethyl)-2-methyl-aniline yellowish red 5 N-(B-cyanoethyl)-2,5-dimethyl-aniline red 6 N-(B-cyanoethyl)-2-ehloro-aniline yellowish red 7 N-(p-cyanoethyl )-2-methoxy-aniline red 8 N-(B-cyanoethyl-2-methoxy-5-methyl-aniline red 9 N-butyl-N-(B-chloroethyl)-aniline bluish red l0 Nethyl-N-( #chloroethyl )-3-methyl-aniline blue-red l l N-ethyl-N-benzyl-aniline red l2 N-ethyl-N-( fi-phenylethyl )-aniline red l3 N-(B-hydroxyethyl)-aniline bluish red I4 N-butyl-N-(flhydroxyethyll-aniline bluish red 15 N N-bis-(B-hydroxyethyl)-3-methyI-aniline blue-red l6 N-(B-hydroxyethyl)-N-(B-cyanoethyl)-aniline yellowish red 17 N-(fl-acetoxyethyl)-N-(B-cyanoethyl)-aniline yellowish red l8 N,N-bis-(B-acetoxyethyl)-3-methyl-aniline red 1 I9 N,N-his-(fl-methoxycarbonyloxyethyl)-aniline yellowish re 20 N-(B-carbomethoxyethyl)-aniline re 21 N-(B'carbomethoxyethyl)-N-(fl-cyanoethyl)- yellowish red niline 'ontinued No. A B

85 l-ethyI-3-cyano-4-m ethyl-6-hydroxy-pyridoneorange (2) 86 2.6-dihydroxy-3-cyano-4-methyl-pyridine orange 87 l-phenyl-3methyl-pyraz0lone-( 5) yellow 88 l Bhydroxyethyl )-3-methyl-pyrazolone-( 5 yellow 89 Lphenyl-pyrazolone-(S )-carboxylic acid-(3)- yellow ethylester 90 l-butyI-4-hydroxy-q uinoline-( 2) yellow 91 2-methyl-indole orange 92 2- henyl-indole orange 93 lE-dimethyl-indole orange 94 l-methyl-Z-phenybindole orange 95 2,6-di-( methylamino )-4-phenylamino-pyrimidine red 96 Z-phenylamino-4-methyl-thiazole bluish red 97 2-methylamino-4-phenyl-thiazole bluish red 98 3 .7-dihydroxyl ,2 ,3 ,4-tetrahydro-benzol h quinoline green 99 N-(B-cyanoethyl)-3-methyl-aniline yellowish red I00 N-(B-cyanoethyl)-3-methoxy-aniline yellowish red lOl N-(B-cyanoethyl)-3-ethoxy-aniline yellowish red I02 N-(B-cyanoethyl)-3-chloro-aniline yellowish red 103 N-(fi cyanoethyl)-3-acetamino-aniline red 104 N-butyl-N-(,B-acetoxyethyl)-aniline red I05 N-ethyl-N-(fi-acetoxyethyl )-3-methyl-aniline red I 06 N,N-bis-( B-methoxyethyl )-3acetylamino-aniline blue-red 107 N,N-bis-(B-ethoxyethyl )-3-acetylamino-aniline blue-red 108 N ,N-bis-(fl-methoxyethyl )-3-methoxy-carbenylamino-aniline blue-red l 09 N-ethyl-N-benzyl-3-acetylamino-aniline blue-red l 10 N-methyl-N-benzyl-3-methoxy-carbonylaminoaniline blue-red l l l N-ethyl-N-(B-methylaminocarbonyloxyethyl)- aniline red 1 l2 N-ethyl-N-(B-phenylaminocarbonyloxyethyl)-3- d methyl-aniline When the diazo component used in Example l (b) is replaced with equimolar amounts of one of the compounds listed below and the resultant diazonium salts in Example 1 (b) or in the preceding Table, then very valuable dyestuffs are again obtained, which dye polyester fibres in the shades given for the respective couare coupled with the coupling components mentioned 35 pling components.

GH3SO2 N ind-m CN CN N I N J- N112 Emmplc rinsing and drying, there results a clear strongly bluish 0.1 g of the well dispersed dyestui'l of the formula 20 red dyeing of good fastness to wet processing and light.

is introduced at 40C into 1 litre of water containing, Example 5 (b) in addition, 0.2 g sodium dinaphthyl-methane- 10,6 g f th thiodiazole of the formula sulphonate as well as 0.3 g cresotic acid methyl ester.

g ofa fabric of polyethylene terephthalate are introduced into this bath, the temperature of the dyebath is C raised to 100C within about 20 minutes, and dyeing is carried out at the same temperature for 60 90 minutes. A strong red dyeing of good fastness to wet processing, sublimation and light is obtained.

are dizizotised with 7.5 ml of 41.2 percent-strength nih the Substrate replaced m present Exam trosylsulphuric acid in a mixture of 160 ml of glacial 10 a fabnc of Cellulose macctme h acetic acid and 80 mlof propionic acid. For diazotisaclcar red dye ng of good general fastness properties is tiuny'thcrc is added at to 3 Solution of 153 g kcwlsc l2-(N-ethyl-N-phenylamino)-ethyll-benzyldimethylammonium chloride in ml of glacial acetic Example acid. After 30 minutesy the mixture is poured with stir- 0.l g of the dyestuff of the formula ring on to 200 g of ice. gradually diluted with 500 ml are introduced in well dispersed form at 40 50C in of ice-water; the pH of the solution is adjusted m 4 to 1 litre of water containing, in addition, 0.5 g ofa sul- 5 at a maximum t m er t re 10C. and th re ult nt phite cellulose decomposition product. 20 g Ofll yarn rcd dycstuff is salted out with sodium chloride, The of poIy- -CHP I are introduced into this bath, the precipitate is filtered oftwith suction, washed with a 10 temperature is raised to C within about 20 percent di hl id solution d d i d Th dminutes and dyeing is carried out for l hour. After 65 m re ond t the formula 0.5 g of the dyestuff obtained are dissolved in 3 litres There results a clear red dyeing of excellent lustness of water with the addition of3 ml of 30 percent acetic p p f" acid. 100 g of polyacrylonitrile yarn are introduced into Dyestum of 51mm" properties are obtained when the I 0 l5 diazonium salt prepared in the present Example is comthis bath at 40 50 C, the temperature of the dyebuth is raised m mooc Within about 40 minutes and dyeing A of the following Table. The shades of the dyestuffs is carried out at the same temperature for about l hour. on acrylic fibres are given in Column B;

figs A B 2 5 635 1 N Q r e blue-rod OH2-GH2-N-GH2 01 033 2 5 6 c1 2 N 9 blue-red \CHZ-GHQ-N- (011 5 2 5 9 5 @N 6 Br red cn -cn N- (01 5 2 5 e 4 N 01 red Q cn -cn -ni 0 a 5 on s N O. 5 el red Olig-OHz-F-Ofia 9 i 6 on -0H -0H 4mm zncl blue-rod rad hined with the coupling components listed in Column 

2. Azo dyestuff of the formula
 3. Azo dyestuff of the formula
 4. Azo dyestuff of the formula
 5. Azo dyestuff of the formula 